Mothproofing compositions and their manufacture



Patente d Dec. 30, 1941 UNITED STATES PATENT OFFICE MOTHPROOFING COMPOSITIONS AND THEIR MANUFACTURE Henry Martin, Basel, and Hans Heinrich Zaeslln,

Riehen, near Basel,

Switzerland, assignors to the firm J. R. Geigy S. A., Basel, Switzerland No Drawing. Application April 21, 1939, Serial No. 269,216. In Switzerland January 13, 1937 -7 Claims.

This application is a continuation in part of our application Ser. No. 184,274, filed January 10,

1938; We have found that colorless condensation products derived from cyanuric' halides by substituting for their halogen atoms 2 or 3 organic' with the cyanurip halides there may be used.

aliphatic, araliphatic or aromatic compounds of the benzene series, containing one exchangeable hydrogen atom adapted to react with a halogen atom of the cyanur'ic trichloride but no auxochromic group or other groups which would impart color to the condensation product. It is preferable that at least one of the used organic compounds contains a radical of an aminodiphenylether.

Moreover it is a condition for the final product that it contains at least one halogen atom and at least one sulphonic acid group; both these substituents may already be present in the compounds that react or may be introduced afterwards into the. condensationproduct obtained from the cyanuric halide andthe compounds with reactive hydrogen. But also halogenated and/ or sulphonated condensation products may be further treated .with halogenating and/or sulphonating'agents to raise the halogen contents or to improve the water-solubility.

One halogen atom of the cyanuric compound may also be retained or exchanged for an inorganic residue such as --NHz or -OH.

whese condensation products may be obtained according .to known processes '(see for example Chem. Centralblatt 1925, II, pages 775-781), by causing for example cyanuric trichloride to react in presence of an agent that binds hydrogen halide such as sodium acetate or alkali carbonate with the compound having reactive hydrogen, for example an amine, a phenol, an alcohol or a mercaptan. Y

To obtain a particularly good effect, it is prefer able-to use halogen-substituted and/or alkylated aromatic amines, also sulphamides, substituted phenols and mercaptans.

The new compounds are capable, when applied according to dyeing processes, of protecting wool against moths and like insect pests.

tion :.v

EXAMPLE 1 1 molecule of cyanurlc trichloride is condensed with 1 molecule of 2-amino-4:4-dicl'lloro-1:1'- diphenyl-ether-2'-sulphonic acid (obtained by sulphonation of the 2-amino-4:4'-dichlor0diphenylether), 1 molecule of 3:4-dichloraniline and 1 molecule of 1-amino-3:4-dichlorobenzenefi-sulphonic acid., A quantity of the condensation product thus obtained corresponding with 3 per cent of the goods to be treated is dissolved in water (bath concentration 1:40) and mixed with 4 per cent of sulphuric acid and 10 per cent of Glaubers salt, both calculated on the goods to be treated, whereupon loose wool or textiles of animal fibres are impregnated in this solution while boiling during one hour. Finally the goods are rinsed and worked up in the usual manner. They have thus become moth-proof.

In the above example there can also be used with a similar result the condensation products mentioned in the following table:

Condensation product of 1 molecule of .cyanuric trichloride with- 1 mol. of-

1 mol. oi- 1 mol. of-

2:4-dichlorophenol-6-sulphonic aci i-amino 4' chloro or bromo 1:1 -diphenyl- 2:4-dichloro-phenol-6-sulphonic acid- 4-amino- 4'-ohloro-3 5 -dimethyl 1:1-diphenylether-Z-sulphonic acid.

1-amlno-2: i-dichlorobenzene-fi-sulphonic acid 2-sulphonic acid, prepared irombalogenated crudexylenol. f I

ether-Z-sulphonic acid. v

4 kamahioy-chloro-l:1'-diphenyletlier-2sulphon- 3:4-dichloraniline l-amino-3:4-dlchlorobenzene-6-s1flph0nic aci 5.1--. azi-dichlorophenol-o-sulpbonic acid.- NH 4 amino 4' 011101; n iietbyl 1:1 die let er-2-sul o caci. 6 2 amino 3' methyl 4' chloro 1:1 di- 3:4-dicbloraniline or 4-,bromaniline..- p 1 3 3? p phenylether-d-sulphonic acid.

7. 2-amino-4-sulpho-Q-chlorodiphenyl-sulphide..- .'do Do.

8- 4 amino 3' methyl, 4 chloro 1:1 di- -4-a'mi1io 4' chloro -,1:l' diphenyl 4-cblorobenzene-sulphamide.

plienyletliem-sulphonic acid. ether-2-sulphonic acid.

o an dn 3:4-dichlorobenzene sulphamide.

- 1 nor a su as I e Bromoor chloro-xylyletber oi 4-sri1inophen'ol- .do y age 1-amino-3:4 -'dichlorobenzeue-6-sulpbonic acid.

The following examples illustrate the invenaration may Into 9.3 parts by weight of finely divided cyanuric trichloride obtained for example by pouring a solution thereof in 50 pai ts of acetone 18 be given:

of 22 parts water.

Condensation product of 1 molecule of cyammc trwhloride unth- No. 1 mol. oi'- 1 mol. oi- 1 mol. oi-

l2..-. 3:4-dichlorophenol-6-sulphonicacid NaOH 4-amino-4'-chloro-5'-methyl-1:l{-diphenylether-2-sulphonic acid. 13..-. 3:4:6-trichlorophenol-Qsulphonicacid Aniline Do. 14.... Mcta-chloraniline 2-alfilingi-k4 aiichloro-l-l-diphenyiether-2-sulp on cam 15..-. 2:4-dichlorophenol-6-aulphonic acid 3:4-dichloraniline Do. 16... l-ammo-la-dlchlorobanzene-fi-sulphonic acid. -do 44min?-2:4':%trichloro-l:l-diphenylether-2- sup onic ac 17.-.. do .-do 2-amino-2':4:5-trichloro-l:l-diphenyleter-4- sulphonic acid. 18..-- 3:4-dichloranilina NaOCQEh iamno-fl-chioro-l:1-diphenylether-Z-sulphonic' acx 19.-.. ...-.do Dimethylamine Do. 20.... 3:4:6-trichloranilina NaOCH: 2-amino-4:4-dich1oro-1:l-dipheny1ether-2-sulphonic acid. 21..-- -.---do NH Do. do Na0H.. Do. do 2-amino-4:4'-dichi Unchanged.

' ether-2-sulphonic acid. 3:4-dichloram1ine NH; 2-amino-4:4-dichioro-l:l'-diphenylethcr-2'-suiphonic acid. ..-.do. NaOH Do. 3:4:5-tnchloraniline 3:4:gatrichlorophenol-Z-sulphonic Do.

ac 28.... Aniline.- do Do. 29---. 3:4:5-trichloraniline 3:5-dimethyl-i-chlorophenoi-Z-sui- Do.

phonic acid. 30.... 4-chioraniline do Do. 31.... 3:4:5-trichloraniline'. Ii-fitjhyi-d-chlorophenol-G-sulphonic D0.

/CH: 32..-- 4-amino-2:4'-dichloro-5'-methyl-1:l'-diphenyl- H.N 4-amino-2:4'-dichioro--methyl-l:l'-diphenylethet-2'-sulphonic acid. \Cm ether-Zsulphonic acid. 33.--- 3-methyl-4chlorophenol-6-eulphonicacid NaOK 4-amino-3: 5-dimethyl-4'-chloro-1:l'-diphenyiether-2-sulphonic acid; 34--.. NaOCH; 4-chloro-4'-amino-1:1-diphenyl- 4-chlor9-4-amino-l:1-diphenylether-2'-suiether-W-suiphonic acid. phonic acid. 35.... NaOH do D0. 36...- NaOCH; 2':4-diehloro-5-methyl-4'-amino-1:1'- 2':4-dichloro-5-methyl-4-amino-l:l-diphenyidi henylether-Z-sulphonicacid. ether-:z-sulphomc acid. 37.-.. 3:4- aniline 4 orofifl-ranmimfiky-diphenylether- 4-ichlo lg-2-amino-l:1-diphenylether-4'sulphono cac caci 39..-- NaOH l-chlogo-a methyl-i-amino-l:1'-di- 4'chloro-3-methyl-4-amiho-l:l'-diphenyletherphenylether-zaulphonic acid. 2-sulphonic 801d. 40..-. UnchangedorNaOCflI; d'-chloml;4-:jmi:g-dl:l-diphenyletheri chlo rg-iamino-l:l-diphenyiether-2-sulphonfl-sul o c 10 ac 41..-. 3:4-dichloranlline szidicgloraniljm 4-cli]iiorio-2-ag1ino-l:1-diphenylsuiphide-4-sulp on cam 42...- NaOH 4'-chioro-4-amino-3:5'-dlmethyl-1:l'-- 4'-chloro.-4-amino-3:5-dimethyl-l:l-dipheny1- di henyleiher-mphonic acid. 'ether-Z-sulphonic acid. 43.... 3:4:5-trichloraniline...- Na(?CH- 4-ghlo ig-4-amino-l:1-diphenylethei-2-sulphonaci 44..-. 3:4-dichloraniline 3:4-dichlonnlllne 4'-chloro-4-amino-3-methyl-l:1-diphenyletherzsulphonic acid. 45.--- 3:4:5-trichloraniline 3:4:5-trichloraniline Do. 46..-. NaOH 4:4-dichloro-2-amino-l:l-diphenyl- 4-chloro-i-amino-W-methyl-l:1-diphenylether ether-f-auiphonic acid. Z-sul honic acid. 47.--. 3:4-dichloranih'ne a NaOCH, 2:4-dic oro-3':5-dimathyl-4-amino-1:1'-diphenylether-2-suiphonic acid. 48.-.. Sodium-n-propyiate 2-amino-4:4'-dichlom-l:1'-diphenyl- 2-amino-4:4-dichloro-l:l-diphcnylether-2-sulather-f-aulphonic acid. phonic acid. 49..-. Sodium-isopmpylato 2-amino-4:4'-dichlom-l:1'-diphenyl- Dov ether-f-mlphonic acid. Sodium-n-butylata do Do. Bodium-iaobutylatado Do.

Sodium-isoamylate do Do. NaOH 2:4':5'-n'ichlom+amino-l:1'-diphen- 2:4:5'-trichloro-4-ammo-l:1-d1phenyl-ether-2'- yiether-f-sulphonic acid. sulphonlc acid. ....-do 2:4-dichlomphenol-6-sulphonic acid.. l-czilglxol-l -rnethgl-i-ammo-l:1'-diphenyletherp omc aci .-..-do 4'-chloro+amino-l:l-diphenylether- 4:4'-dichloro-2-amino-1:l-diphenyiether-2'-sul- 21ml honie acid. phonic acid. NaOCH; kd'dkglomphenolo-sulphonic acid- 4-ichlolrg-i-amino-l:l'-diphenylethei-2'sulphoncac .-..-do Do. Dimethy do Do. i-chloranilina ..---do 4:4'-dichlom-2-amino-I:l-diphenylcther-2'-sulphonic acid. 3 4-dichloraniline do Do. 3 4 o-trichloranilino do Do. 2:4:6-trichloraniline fin Do. NaOCH; 4-mcthyi-4-amino-1:l'-diphenyi- 4-chloro-4-amino-1:l'-diphenylethcr-2-sulphonether-2m] nicacid. ic acid. NaOH 4:4:5-trichloro-5'-methyl-2 amiuo-1:l'-diphenyiether-Zsuiphonic acid. ..do 4'- hl0m+amlno-l:l'-diphenyiether- 4'-chlom-'4-amino-lzl-diphenylsulph0ne-2-sui- Q-auiphonic acid. phonic acid.

into 200 parts of water, there is introduced drop by drop at 0 C., while well stirring, a solution of 2-amino-4:4'-dichloro-1:lj-di- 70 phenylether-2'-sulphonic acid in 200 parts of The stirring is continued until all the cyanuric trichloride has disappeared, which will be the case after about half an hour. At the same time the liberated hydrochloric acid is neutralised by means of the necessary quantity of sodium carbonate. Thereupon, a solution of 8.1 parts of 3:4-dichloraniline in 70 parts of acetone is introduced drop by drop at 30-40 0. Then the mass is stirred for to 1 hour while gradually neutralising by means of a sodium carbonate solution the mineral acid produced, the total con,- sumption of sodium carbonate being the theoretically necessary quantity. Thereafter the tem perature is raised to 85-90 C. and a solution of 14.5 parts of 1-amino-3:-dichlorobenzene-G- sulphonic acid of 83 per cent strength in 200 parts of water and the necessaryquantity of sodium carbonate is slowly added.

The mixture is stirred until the reaction is achieved, the progress of the operation being fol- (b) 16.3 parts of the condensation product of Example 3a are dissolved with the calculated amount 01 sodium carbonate in 400 parts of water; this solution is treated at,30-40 C. with chlorine gas for 2 hours. By adding dilute sodalye in drops, the reaction is kept slightly alkaline to litmus. Finally the chlorinated compound is precipitated by the addition of a mineral acid. Chlorine content 8.5 per cent,

By a chlorination of 6 hours a chlorine content of 16.3 percent is obtained.

(c) 14 parts of a condensation product made from 1 mol. of cyanuric chloride, 1 mol. of sodium methylate, 1 mol. of 4-amino-l:1'-diit phenylether-2-sulphonic acid and 1 mol. of 3'- lowed or observed through the course of neu- EXAMPLE 2 (.S'ulphonation of an insoluble condensation product) 15 parts of the condensation product made from 1 mol. cyanuric chloride, 2 mol. of 4:4'-dichloro-2-amino-l:1-diphenylether and 1 mol. of NaOH are added in portions while stirring to 150 parts of sulphuric acid monohydrate and the whole is heated to 60? 0., till a test portion is (ll-Ha soluble in dilute sodium carbonate solution. This is the case after about hour. The whole is poured on ice, the sulphonic acid is salted out, filtered with suction and dried.

EXAMPLE 3 (Halogenation of condensation products) (a) 32.6 parts of the condensation product, obtained by condensing 1 mol. of cyanuric chloride with 2 mol. of 3-methyl-4-amino-1:l'-diphenylether-2-sulphonic acid and 1 mol. of NaOI-I are dissolved in 400 parts by volume of glacial ci-Osm+ox acetic acid and 200 parts by volume of conc. hydrochloric acid and 100 parts of a solution of 10 per cent strength of sodium chlorate dropped in at C. during 5 hours. The increasing precipitation is finally completed by the addition of methyl-4-amino -1:1 diphenylether-2-sulphonic acid are dissolved in 500 parts of water and chlorine is passed into the solution for 3 hours at 20-30 .C. The free acid of the chlorinated product separates in the form of slightly yellow crumbs. It is soluble in water, more easily in dilute sodium carbonate solution. Chlorine contents 24.1 per cent or about 6 atoms.

Similar halogenated products are obtained by interrupting the chlorination after some time, for example after 2 hours and halogenating further in glacial acetic acid or in a solution in chloroform with the calculated amount of bromine.

The above enumerated reaction-compounds, in so far as they are new, are made according to known methods, for example the aminodiphenylether of No. 2 in the third column of the preceding table, according to the following equation:

SOQNB (3H3 SOaNa and by reduction of the nitro-group according 45 to Bchamp (see for example German Patent 156,156 or U. S. Patent 1,042,198).

The diphenylether sulphonic acid of No. 14 of the table may be made by sulphonation of 2 amino 4:4 dichloro 1:1 diphenylether with conc. sulphuric acid at 100 C.

The diphenylsulphide-sulphonic acid of No. 41

of the table may be made in a manner analogous according to the equation:

1000 parts of water. When filtere'd with suction and by usual reduction of the nitro-group.

The diphenylsulphone-sulphonic acid of No. 65 of the table can be made in known manner (alkali-salts of aromatic sulphonic acids reacted with aromatic intro-compounds containing exchangeable halogen) according to the equation:

and dried, the new product. a bright powder, is soluble in water, but mpre easily soluble in dilute solution of sodium carbonate. Its chlorine content is about 20 per cent.

SOaNa SOaNa and by usual reduction of the nitro-group.

By compounds of the benzene series applicants mean in the following any colourless com- 5 pound which contains at least one benzene nucleus, therefore also compounds with several benzene nuclei, provided that the same are not condensed with each other.

What we claim is:

1. Moth-proofing compositions containing as their essential active ingredient a compound of the general formula wherein X1 and X2 represent two radicals of the benzene series, and wherein Y represents a radical selected from the group consisting of aliphatic amines and aromatic amines of the benzene series, of mercaptans of the benzene series and of monohydric compounds of the formula ROH, R being one of the group consisting of H, alkyl and phenyl, the three radicals X1, X2 and Y being connected each by one of the group consisting of O, N and S with the cyanuric nucleus, and the benzene nuclei of X1, X2 and Y containing substituents selected from the group consisting of H, Br, Cl, phenoxy, chlorophenoxy, alkylphenoxy, phenylthio, chlorophenylthio and a1 kyl, at least one of the three radicals X1, X2 and Y hearing at least one sulphonic acid group and at least one halogen atom, and at least one of the three radicals X1, X2 and Y being an aminodiphenylether radical, the compositions being colorless to nearly colorless powders which are soluble in water and very eflicacious in protecting wool, hair, fur, feathers and the like against moths and other insect pests.'

2. Moth-proofing compositions containing as their essential active ingredient a compound of the general formula wherein X1 and X2 represent two identical radicals of the benzene series, and wherein Y represents a radical selected from the group consisting of aliphatic amines and aromatic amines of the benzene series, of mercaptans of the benzene series and of monohydric compounds of the formula ROH, R being one of the group consisting of H, alkyl and phenyl, the three radicals X1, X2 and Y being connected each by one of the group consisting of O, N and S with the cyanuric soluble in water and very, efllcacious in'protecting wool, hair, fur, feathers and the like against moths and otherinsect pests.

3. Moth-proofing compositions containing as 5 their essential active ingredient a compound of the general formula X1 N x:

wherein X1 and X2 represent two radicals of aminodiphenylethers and Y represents a radical selected from the group consisting of aliphatic amines and aromatic amines of the benzene series, of mercaptans of the benzene series and of monohydric compounds of the formula ROH, R

being one of the group consisting of H, alkyl and phenyl, the two radicals X1, X2 being connected by N and the radical Y by one of the group consisting of O, N and S with the cyanuric nucleus, and the benzene nuclei of X1, X2 and Y containing substituents selected from the group consisting of H, Br, Cl, phenoxy, chlorophenoxy, alkylphenoxy, phenylthio, chlorophenylthio and alkyl, at least one of the three radicals X1, X2 and Y bearing at least one sulphonic acid group and at least one halogen atom, the compositions bethe general formula XI N X2 c wherein X1 and X: represent the radicals uf the same amino-diphenylether and Y represent; a radical selected from the group'consisting of aliphatic amines and aromatic amines of the benzene series, of mercaptans of the benzene series and of monohydric' compounds of the formula ROH, R being one of the group consisting of H, alkyl and phenyl, the radicals X1, X2 being connected by N and the radical Y by one of the group consisting of O, N and S with the cyanuric nucleus, and the benzene nuclei of X1, X2 and Y containing substituents selected fromthe group consisting of H, Br, Cl, phenoxy, chlorophenoxy, alkylphenoxy, phenylthio, chlorophenylthio and alkyl, at least one of the three radicals X1, X2

and Y bearing at least one sulphonic acid group and at least one halogen atom, the compositions being colorless to nearly colorless powders which are soluble in water and very efllcacious in protecting wool, hair, fur, feathers and the like against moths and other insect pests.

5. A moth-proofing compound corresponding in the free state to the probable formula:

AOuNl 'sOsNa the compound being a colorless to nearly color- '7. A moth-proofing compound corresponding less powder which is soluble in water and is very in the free state to the probable formula:

O CzHs t i N/ \1;I I

some some efiicacious in protecting wool, hair, fur; feathers the compound being a colorless to nearly colorand the like against moths and other insect pests. less powder which is soluble in water and is very 6. A moth-proofing compound corresponding efilcacious in protecting wool, hair, fur, feathers in the free state to the probable formula: and the like against moths and other insect pests.

(l).CHs

the compound being a colorless to nearly colorless powder which is soluble in water and is very HENRY T v efficacious in protecting wool. hair, fur, feathers HANS HEINRICH ZAESLIN. and the like against moths and other insect pests. 

